Note: Descriptions are shown in the official language in which they were submitted.
~8.~l4
ANTISTATIC N-HIGHER ALKYL AND ALKENYL NEOALKA~OAMIDES,
PROCESSES FOR MANUFACTURE THEREOF, ANTISTATIC COMPOSITIONS
CONTAINING SUCH AMIDES, AND PROCESSES FOR DECREASING
ACCUMULATIONS OF STATIC CHARGES ON LAUNDRY
,
This invention relates to novelalkanoamides which have
been found to be adsorbable from wash and rinse waters by fibrous
materials, such as the fabrics of items of household laundry,
especially synthetic polymeric fibers thereof, such as poly-
esters, and which have been found to impart to such fabrics
antistatic properties, so thatthe accumulation or the develop-
ment of electrostatic charges thereon is inhibited. More partic-
ularly, this invention is Of: N-higher alkyl and alkenyl neoalkano-
amides of 5 to 16 carbon atoms in the acyl moieties thereof and
8 to 20 caxbon atoms in the alkyl and/or alkenyl groups of the
amine moieties thereof, such as neodecanoamides, neopentano-
amides, neoheptanoamides, neononanoamides, neododecanoamides, neo-
tridecanoamides and neotetradecanoamides; methods for their manu-
facture; detergent, rinse and other antistatic compositions and
products containing them; and methods of treating laundry with
such compositions in washing, rinsing and other operations to
impart antistatic properties to it.
Neodecanoic and neopentanoic acids are presently being
marketed by Exxon Chemical Americas and are described in a bulletin
issued by such company and entitled Neo Acids Properties, Chemistry
and Applications (copyright 1982). Other neoalkanoic acids have
also been made, such as neoheptanoic acid, neononanoic acid and
mixed neododecanoic, neotridecanoic and neotetradecanoic acids.
Amides of neo acids and methods for their manufacture are referred
l4
to broadly at page 10, column 1 of such bulletin, and uses of
various neodecanoamides are mentioned therein, including appli-
cations as pesticides, plasticizers (for polyvinyl chloride),
foam boosters, foam suppressants, and slip agents (for polyolefin
S films). However, no mention is made of any of the neoalkanolamides
of the present invention and the preferred manufacturing method,
which results in the production of light colored, better product,
is not taught, nor are they suggested for use as antistats.
Computer searches of V.S. patents for the period 1950-
1984 and of Chemical Abstracts for the period 1967-1985 have
resulted in the finding of U.S. patent 4,440,666,directed to a
hydrocarbon liquid containing a minor proportion of a reaction
product of a polyalkylene polyamine and a neo-acid of 5 to 20
carbon atoms, in which the amide acts as a corrosion inhibitor.
This patPnt does not appear to disclose any N-higher alkyl or
alkenyl neoalkanoamide and does not suggest that any such com-
pounds would have antistatic properties. None o~ the other refer-
ences found in the computer search discloses or suggests N-higher
alkyl or alkenyl neoalkanoamides, any antistatic properties of
such or closely related compounds, or their inclusion in detergent,
rinse or other laundry treating compositions, and none discloses
or suggests applicants' process for manufacturing such amides of
better color (and higher purity).
~ecause modern synthetic organic detergents are excel-
lent cleaning agents and, unlike soaps, do not normally leave
deposits of fatty materials on washed laundry, often laundry
washed with them lacks desirable softness. Because synthetic
polymeric fibers, which are the fibers of the fabrics of
much of ~uch laundry, are susceptible to disadvantageous
accumulations of static charges, which occur during machine
drying or when the fabrics are rubbed against other materlals,
S with such tendency to static accumulation and resulting
discharging or sparking being exacerbated by the absence of
any fatty acid or insoluble soap coating on the fibers, much
research has been conducted in an effort to discov~r materials
which, when incorporated in detergent compositions or in
rinse waters, would diminish any static charges on the
laundry or would inhibit the accumulation oS such charges.
Quaternary ammonium salts, such as di-lower alkyl di-
higher alkyl ammonium halides, e.g., dimethyl distearyl ammonium
chloride, have been used as fabric softeners in detergent~, in
?5 fabric softening compositions for addition to the rinse water,
and in papers, sponges and other substrates intended for introduc-
tion into laundry dryers,where they transfer such cationic mate~i-
al~ to the laundry being tumbled. Certain amines have also been
found to be useful in some such applications. However, because
such cationic materials react objectionably with anionic deter-
gents their use in anionic detergent compositions results in pro-
duction of undesirable reaction products and causes losses of
detergency.
It is an important feature of the present invention
that certain amides have been discovered which are water
insoluble and which may bein desired oily or plastic, flowable
or spreadable state at normal use temperatures, e.g., 10 to
90C., preferably 10 to 60C. Particular amides which have
the desired physical characteristics, are adsorbable or otherwise
- 1~98;~l4
depositable onto laundry from the wash water or rinse water in
a washing machine, or can be deposited onto drying laundry in
the dryer, are higher amides of neoalkanoic acids. In accord-
ance with the present invention such novel compounds are N-
higher alkyl and alkenyl neoalkanoamides of neoalkanoic acids,such as amid~ previously mentioned,the acid moieties ~f which have
5 to 16 carbon atoms andpreferably contain from 7 to 14 carbon atoms.
Although some branching of the hydrocarbyls is acceptable
under certain circumstances, it is preferable that the alkyl
and alkenyl groups be substantially or essentially linear, and
more preferably, they will be linear. Among the more prefer-
able of the neoalkanoamides are those wherein the alkyl or
alkenyl is higher, of 8 to 20 carbon atoms, often preferably 12
to 18 carbon atoms, such as may be derived from coconut oil,
tallow or hydrogenated tallow, which for the higher alkyls are
herein referred to as coco alkyl, tallow alkyl and hydrogenated
tallow alkyl, respectively. It should be noted that in this
usage "alkyl" may be inclusive of hydrocarbyl groups contain-
ing minor unsaturation, as in tallow alkyl, which contains a
minor proportion of a monounsaturated C18H35 group- Also with-
in the invention are: a process for the production of such N-high-
er alk(en)yl neoalkanoamides; detergent compositions comprising
N-higher alk(en)yl neoalkanoamides; detergent compositions
containing such a neoalkanoamide and a fabric softe~ing
proportion of bentonite; rinse compositions containing both
such constituents; a substrate material containing such a
neoalkanoamide, for use in a laundry dryer; and processes for
treating laundry with the neoalkanoamide during washing, rinsing
and/or drying.
8~4
Neodecanoic acid, which is available commercially
~rom Exxon Chemical Americas in prime and technical grades,
i~ synthesized by reacting a branched nonene and carbon
monoxide under high pressure at an elevated temperature in
the presence of an aqueous acidic catalyst (Xoch reaction).
The general mechanism involved includes generation of a
carbonium ion followed by complexation with carbon monoxide
and the catalyst to form a "complex", which is subsequently
hydrolyzed to generate the free acid. The formula of the
free acid is:
R'
R-C-COOH
wherein the number of carbon atoms in R + R' + R" is 8; about
31~ of the neodecanoic acid is of a structure wherein R' and
Ru are both methyl and R is hexyl; 674 is of a formula
wherein R' is methyl, R" is of a carbon atoms content greater
than that of methyl and less than that of R, and R is of a
carbon atoms content less than that of hexyl and greater than
that of R"; and 2~ is of a formula wherein R' and R" are both
of a carbon atoms content greater than that of methyl and less
than that of ~, and ~ is of a carbon atoms content less than
that of hexyl and greater than those of ~' and X". The dissocia-
tion constant (Ka~ of neodecanoic acid is 4.20 x 10 6. Among
other neoalkanoic acids that are available may be mentioned
others in the 5 to 16 earbon atom content range, such as noo-
p~Atanoic, neoheptanoic, neononanoic, neodecanoic, neodo-
decanoic, neotridecanoic~and neotetradecanoic acids
To make the neoalkanoamides of this invention the
neoalkanoic acid, such as neodecanoic acid, may be reacted
8;~4 ~
directly with a higher alkyl- or alkenyl-amine, which is very
preferably a linear primary amine, R"'NH2, but also may include
slightly branched alkyls having less than 10 or 20% of their
carbon atoms contents in branch(es), e.g., as in 2-methyl hepta-
decane. The higher alkylamines and alkenylamines employed willnormally be of a number of carbon atoms in the range of 8 to 20,
often preferably 12 to 18, but may include compounds of more or
fewer carbon atoms too, providing that the amides made possess
the desired properties, as described herein. Among the more pre-
ferred of the amine starting materials are coco alkyl amine,tallow alkyl amine (which contains a minor portion of oleyl amine),
and hydrogenated tallow alkyl amine. Such materials are avail-
able from vegetable and animal sources, and amides made from
them have been found to be excellent antistats,which are compa-
tible with anionic detergents. Also especially useful amine start-
ing materials are oleyl amine and octyl amine.
The invented amides, which are of the formula:
R'
' H
R-C-CON-R'~
R"
for the neodecanoamides, may be made by reacting a neoalkanoyl
chloride with a higher alkyl or alkenyl amine, R"'NH2, but a less
costly synthesis is directly from the neoalkanoic acid by react-
ing it with such amine at an elevated temperature. The product
of such reaction, unfortunately, is often very dark in color,
which can make it unsuitable for incorporation in desirably white
detergent compositions, which would be discolored by the presence
of the amide. Applicants have found that by reacting the neo-
alkanoic acid with the higher alkyl or alkenyl amine, e.g., coco
alkyl amine, at a suitable elevated temperature, preferably about
250C. for the coco-neodecanoamide, under an inert gas or nitro-
gon atmosph~re, ~ nearly w~ter whlte olly product results ~th~
desired amide) which constitutes a first, upper phase, and may be
readily separated from a second, lower phase, which includes by-
products and any excess of reactants.
Normally, the reaction temperature for making the various
neoalkanoamides of this invention will be in the range of 180 to
32~C. and reaction times will be from 5 to 8 hours, with stirring
being continued during the entire reaction. The melting points of
the products will normally be low, so that the prsd~cts will desir-
ably be liquids at room temperature or at normal use temperatures.
~he melting points of the coco alkyl-, tallow alkyl- and hydrogenated
tallow alkyl-neodecanoamides are < OC., 15-17~C. and 45 to 49C.,
respectively while those of the octyl, oleyl, palmityl and stearyl
counterparts are <OC., 5 to 6C., 37 to 38C. and 35 to 40C.,
re~pectively. The refractive indices for the coco alkyl and octyl
neodecanoamides are 1.4626 and 1.4596, respectively. Melting point8
for the other neoalkanoamides of 5 to 16 carbon atoms in the neo-
alkanoic acid will be in the < O to 60C. range and preferablythe amides will be oily liquids at temperatures of 50C. or less,
~nd may be i~ solid state at about room tcmperature,
Although the described N-higher alkyl neodecanoamide~
are the preferred embodiments of the present invention,
other highly branched acids may also be employed for the
manufacture of higher alkyl amide antistats. When neo-
pentanoic acid is employed (it is of the formula
CH3
CH3-C-COOH ),
CH3
1~9~ L4
for the manufacture of N-higher alkyl neopentanoamides
antistatic action i9 obtained but not to the extent realized for
the higher alkyl neodecanoamides. Normally the neoacid employed
will be of 5 to 16, preferably 7 to 14 carbon atoms, and ~uch
acids are obtainable by the described process when highly branch-
ed C4-C15 or C6-C13 olefins are employed as starting materials
in the Koch reaction.
N-Higher alk(en)yl neoalkanoamides of the present
invention may be employed to treat various fibrous materials,
lncluding polyesters, nylons, polyacrylates and acetates,
blends of some or all of such material~ and blends o~ any of
such materials with natural fibers, such as cotton, to
lower the tendencies thereof to accumulate objectionable
~tatic charges. They may also be used to treat non-fibrous
polymeric materials, such as video tapes and cassettes,
camera film and photographs, movie film, sound recording
tapes and cassettes, plastic sheets and molded ~and other-
wise fo~med) plastic items, such as items made from polyYinyl
chloride (or polyvinyl chloride sheeting). In such treat-
ments the amides may be applied directly or in suspension or
solution, as liquids, pastes or sprays, to the surfaces of the
tems to be treated, in comparatively small proportions,
~ormally with the proportion of amide to that of treated
material being in the range of 0.0001 to 0.2%, by weight.
Although the present antistats may be applied
directly or in suspension or solution to materials being
treated to make them static-free it is usually highly prefer-
able for them to be incorporated in other compositions that
are u~ed for different treatments of such material~. Thu~,
it i~ desirable for such antistats to be incorporable in
detergent compositions so that the laundry washed with such
lX~ L4
compositions will not accumulate annoying static charges. Such
compositions will comprise a detersive proportion of a synthetic
organic detergent and a sufficient proportion of an N-higher
alkyl neoalkanoamlde to be antistatic characteristic imparting
to wasned laundry.
The neoalkanoamides of this invention are especially
advantageous for use in detergent compositions of the anionic type
because, unlike quaternary ammonium halides, they do not react
adversely with anionic detergents. Thus, they do not form objec-
tionable fatty reaction products which can deposit onand mar theappearance of washed laundry, and they do not cause a diminution
in detersive activity of the detergent composition. Furthermore,
they are effective antistats, being adsorbable onto washed laundry,
especially synthetic polymeric fibers thereof, during the washing
process. In preferred detergent compositions of this invention
the synthetic organic detergent will be of the sulfate and~or
sulfonate type, normally including a higher aliphatic chain, such
as a higher alkyl of 8 to 20 carbon atoms, in the lipophilic por-
tion thereof. Preferably, such materials will be employed as water
soluble salts, e.g., sodium salts. While the present neoalkano-
amides may be employed in nonionic detergent compositions or deter-
gent compositions of various types, including amphoteric, ampho-
lytic or zwitterionic detergents, preferably the detergent will
be an anionic detergent and will usually be one or more of the
following: linear higher alkylbenzene sulfonates; branched
higher alkylbenzene sulfonat~s; higher fatty alcohol sulfates;
olefin sulfonAtes; paraffin sulfonates; monoglyceride
sulfates; fatty alcohol ethoxylate sulfates; higher fatty
acid sulfoesters of isethionic acid; higher fatty acyl
sarcosides; and acyl- and sulfo-amides of N-methyl taurine.
In such detergents there will normally be present a higher
aliphatic or alkyl group, which is preferably linear, and
which will usually be of 8 to 20 carbon atoms, more prefer-
ably 12 to 18. When lower alkoxy chains are present, as in
the mentioned ethoxylate sulfate, usually there will be from
3 to 30 ethoxies,preferably 3 to 10. Such detergents will
normally be employed as sodium salts although other water
soluble salts, such as potassium, ammonium and triethanol-
amine salts, may be used too, in certain circumstances.
For heavy duty laundering applications the deter-
gent composition will usually contain a builder, to increase
the detergency of the anionic detergent, especially in hard
water. Among the various builders that may be utilized
those of preference include: the polyphosphates, sodium
tripolyphosphate and tetrasodium pyrophosphate; carbonates;
bicarbonates; sesquicarbonates; silicates; sesquisilicates;
citrates; nitrilotriacetates; and polyacetal carboxylates;
all of which are water soluble salts, and the water softening
zeolites, such as hydrated Zeolite A, which are water
insoluble.
The proportion of the invented neoalkanoamide in the
detergent composition will be an antistatic characteristic
-- 10 --
12~8~L4
imparting proportion (to washed laundry ad~orbing the neoalkano-
amide during washing) and such will normally be in the range of
about 1 to 20~ of the detergent compo~ition, by weight, prefer-
~bly being 3 to 15~ and more preferably being 5 to 12~, e.g., about
10~. When heavy loads of laundry are to be treated the content
of neoalkanolamide in the detergent composition will preferably
be about 6 to 10~ or more~ o~e.l 7 to 10~.
In addition to the neodecanoamide, detergent and
builder, the invented detergent composition, even when in
solid or particulate form, will also usually contain some
~oi~ture. The proportion of moisture will usually be in the
range of 2 to 20~, preferably being 3 to 15~ and more prefer-
ably about 5 to 12~, e.g., about 84. The particulate material
will desirably be ln the form of spr~ dried detergent
composition beads, with particle sizes in the range of No's.
10 to 140, preferably 10 to 100, U.S. Sieve Series. Other
forms of the detergent composition may be made, including
liquids, gels, pastes, bars and cakes,and the particulate
compositions and the compositions in such other forms will also
~ormally contain functional and aesthetic adjuvants, and may
contain fillers. Such adjuvants and fillers will normally
compri6e the balances of the detergents. Among the adjuvants
that may be employed are: fluorescent or optical brightening
agents, such as stil~ene brighteners; anti-redeposition
agents, such as sodium carboxymethyl cellulose; soil release
-- 11 --
~l~h98~ 4
promoting polymers, such as Alkaril QCF; fabric softening
agentfi, such as bentonite; anti-gelling agents ~for use in
the crutcher), such as citric acid and magnesium sulfate;
colorants, such as ultramarine blue pigment and dyes; whiten-
ing agents, such as titanium dioxide; enzymes, such as mixedproteolytic and amylolytic enzymes; and perfumes. Among the
fillers or bodying agents th~t are sometimes employed the
most preferred is sodium sulfate, although sodium chloride
ha~ al~o been used. In liquid detergent compositions water,
lower alcohols, glycols, co-solvents and anti-freeze additives
may al80 be present.
The proportions of detergent, builder, N-higher
alkyl neoalkanoamide and moisture in the invented particulata
antistatic detergent will normally be within the ranges of 5
lS to 35~, 10 to 854, 1 to 20% and 2 to 20~, re~pectively.
Preferred proportions are 8 to 30~, 25 to 70~, 3 to 15~ and
3 to 154, respectively, with more preferred proportions being
10 to 25%, 30 to 70~, 5 to 12~ and 5 to 12~, respectively. The
moisture content includes hydrate moisture that is removed by
the standard moisture test, heating for an hour at 105-C., and
~uch removed moisture is not included in the weights of the other
composition components.
The detergent composition, when in particulate
form, may be made by spray drying an aqueous crutcher mix
of the various constituents thereof to free flowing bead
7 ra~ e ~n~f 1~
- 12 -
8;~4 --
~orm, utilizing well known spray drying equipment and follow-
ing a standard spray drying procedure, in which a hot drying
gas, which is the products of combustion of fuel oil or gas,
pas~es concurrently or countercurrently, with respect to
S falling spray droplets of an aqueous crutcher mix, to produce
the dried beads, which are removed from the bottom of the
spray tower, and subsequently may be screened or otherwise
classified to desired particle size range. The beads resulting
are excellent detergents and are capable of having the anti-
~tat component thereof adsorbed by laundry to lower any tendency ofl~undry to accumulate static charges. ~owever, even greater
antistatic activity i8 observable when the neoalkanoamide i8
not 6pray dried with the rest of the detergent composition but
is sprayed onto or otherwise applied to the ~pray dried deter-
lS gent composition particles, ~ase beads or ts~ detergent composi-
tLon made by mixing together particulate components thereof.
In a preferred process the neoalkanoamide is dissolved in ~he
formula proportion of li~uefiable nonionic detergent at elevated
temperature (4D - 50C.) and the solution is sprayed onto and
absorbed by porous spray dried builder beads. ~he mentioned im-
proved antistatic result~ are also obtainable by addition of the
neoalkanoamide antistat to the wash water, with separate addition
thereto of the detergent composition. For such ~nd other use~ the
antistat may be made in a convenient powder form for use by being
1~ 25 fir~t mixed with a suitable carrier, such as Microcel ~a synthetic
calcium silicate powder), a filler, e.g., particulate sodium
sulfate, or a softening agent, e.g., bentonite, or other suitable
~f~de ~
l~B~
material. When liquid, gel or paste detergent compositions
are made, wherein the proportion of solvent or liquid me~ium
18 differentfromthe moisture conten~ of the solid or partic-
ulate products,the proportions of detergent, antistat, builder,
when present, and adjuvants, when present, will be adjusted
accordinsly, normally with the relative proportions thereof
being maintained about the same as in the solid compositions.
However, the proportion of the neoalkanoamide antistat in
such detergent compo~ition~ and iA other antistatic preparation~
will be maintained such as to be capable of imparting antistatic
properties to the material to be treated, when the compoRition
1~ employed in appropriate manner. One of skill in the art
will be able to modify the formulations so as to make products
o~ greatest utility and satisfactory stability. Similarly, it i8
contemplated that the formula will be changed when it i~ desired
to produce compositions useful in the rinse or in the dryer.
Rinse compositions may sometimes contain only the invented
neoalkanoamide dissolved in a suitable solvent medium or
dispersed in an aqueous liquid medium, preferably with the aid
Of a hydrotrope or other surface active component. The prop~r-
tlon of antistat will preferably be kept about the same as that
for the antistatic detergent composition previously discussed, e.g.,
5 to 12%, although less could be used because in the absence
of the detergent and builder the antistat will usually be more
~ubstantive. For liquid preparations for use in the rinse
- 14
lZ~
water, the proportion of solvent or liquid will normally be
from 30 to 90~, while any surface active material or hydro-
trope content will usually be ln the range of 0.1 to 5~. If
quaternary ammonium halide is also present the proportion
~hereof will desirably be in the range of one part of the
quaternary compound tol~ to lO parts of neodecanoamide anti-
stat. Addltionally, when a pol.yurethane or cellulose sponge
strlp or a textile paper substrate is impregnated with the
anti~tat of this invention (usually with the weight percent-
age thereof being from lO to lOO~ of the weight of the sub-
strate), a fatty material, such as monoglyceride or di-
glyceride of higher fatty acids may be present too, to aid in
the depositing of the neoalkanoamide onto the surfaces of the
fabric fibers. A suitable such material is coconut oil fatty
acids diglyceride.
When the invented neoalkanoamide antistat i8
applied to laundry during the washing or rinsinq operation,
by adsorption thereof onto the laundry in the wash water or
the rinse, the concentration of the detergent composition or
the rinse preparation in the wash water will be sufficient
to impart antistatic properties to the washed laundry, e.g.,
laundry items of polyester or polyester cotton blend fabrics.
Such an effective concentration will normally be in the
range of 0.005 to 0.1% of N-higher alkyl neodecanoamide and
preferably such range will be 0.01 to 0.05%. The detergent
i2~
compo~ition or rinse composition concentration i~ the wa~h
wate~ will normally be in the range of 0.05 to 0.5%, prefer-
ably being 0.08 to 0.2~. ~he wa~h or rinse water will
normally be at a temperature in the range of 10 to 90C.,
e.g., 30 to 50C., with the lower part of the 10 to 90C.
washing temperature range being typical of American home
laundry practice and the upper part of that range being that
employed in European practice, especially when perborate-
containing detergent composi~ions are employed kinse tempera-
ture will normally be in the lower part of such range for both).
In American practice the normal washing temperature will be
in the range of 20 to 60C. and for "cold water washing~ and
rinsings such range is often from 20 to 40C. (or lower for
rinsing). The washing operation will normally take between
five minutes and one hour, with rinsing taking from two
minutes to twenty minutes of that time. The water employed
may be soft or hard and hardnesses between 0 and 250 p.p.m.
~mixed calcium and magnesium hardnesses, as calcium carbonate)
may be encountered. Under such washing and/or rinsing
conditions the invented neoalkanoamides are sufficiently
substantive to the laundry being washed, especially that of
~ynthetic organic polymers, such as polyesters, to be adsorbed
th~reon in sufficient proportion to make the polymer anti-
static, thereby diminishing any static charges that could otherwise
accumulate on the polymer during a machine drying (tumbling)
1~!38.~
operation or as a result of frictional forces applied to the
polymer surface, as by rubbing against other materials.
When washed laundry is treated in the dryer with substrate
materials onto which the invented neoal~anoamide or a mix-
ture thereof with quaternary ammonium salt has been depositedit is found that the dried laundry resulting is of a diminished
tendency to accumulate static charges.
While any of the methods of application of the
lnvented neoalkanoamides to material to be treated may be
employed, and good antistatic properties will be transmitted
to the treated material, it is within the invention to
utilize a plurality of such application operations, such as
washing, rinsing and drying, some or all in the presence of
the antistat. Also, laundry may be brushed or sprayed with
the antistat in solution or dispersion, and other materials,
such as carpeting, may be similarly treated. However, a signifi-
cant advantage of the present products is in their compati-
bility with anionic detergents in detergent compositions and
wash waters, wherein antistatic proportions of quaternary
ammonium salts often have undesirable effects on the deter-
Eive action of the anionic detergents and cause objectionable
reactions which often result in spotting with the reaction
products of the laundry or other items being washed.
The infrared absorption spectra for several
representative N-higher alk(en)yl neoalkanoamides are
shown in the drawing, in which:
FIG. 1 is such an absorption spectrum for N-tallow
al~yl neodecanoamide;
FIG. 2 is such a spectrum ~or N-coco alXyl neo-
decanoamide;
FIG. 3 is such a spectrum for N-hexadecyl
neodecanoamide; and
FIG. 4 is such a spectrum for N-oleyl neodecanoamide.
The following examples illustr~te but do not limit
the invention. Vnless otherwise indicated, in these examples,
the ~pecification and claims, all parts given are by weight and
all temperatures are in C.
EXAMPLE 1
181 Grams of Ar~àn CD coco alkyl amine are reacted
with 142 grams of neodecanoic acid ~prime grade, 95.2~ pure)
in a one-liter, 3-necked glass flask fitted with a magnetic
~tirrer, a heating mantle, an ice conden~er, a nitrogen
inlet and a communicating nitrogen source (to blanket the
reaction). Prior to the reaction the flask had been purged
of air and a nitrogen atmosphere had been introduced, which
was maintained during the atmospheric pressure reaction.
The reaction was conducted at 300C. (the reaction range is
from 180-320~C., for this and theother condensation reactions)
and was monitored by observing the water collected from the
condenser. After seven hours it was considered that the
reaction was essentially complete (8 ml. of water had been
d~ /~arl~
-- 18 --
i2.~ 14
collected), and the flask was removed from the heating
mantle. After being allowed to stand at room temperature
over a long weekend ~about 90 hours) the contents were
transferred to a one-liter separatory funnel, washed sequen-
tially with ~ 50:44:6 water:ethanol:HCl ~olution, b) 56:44
water:ethanol solution, c) 5~ aqueous NaOH, and d) distilled
water, until neutral. After completion of washing the
excess water was dralned off and the washed product was dried
in a vacuum rotary evaporator, yielding 273 grams of product.
The product is a light colored oil (Gardner No. 2),
with a melting point less than 0C. and a refractive index
(ND 20C.) of 1.4626. The infrared absorption spectrum for
the N-coco alkyl neodecanoamide made is given in FIG. 1. It
will be noted that at about 3,350 cm. 1 and 1,633 cm. 1
strong absorption bands are present, indicating the presence
in the compound of a secondary amide stretch (N-H~ and a
secondary amide carboxyl (C=O), respectively, and at 720
cm. 1 there is a weak absorption band, indicating the presence
of a long alkyl chain. The nuclear magnetic resonance
spectrum was obtained and was found to be consistent with
the expected structure. A peak in the proton spectrum for
NH appears at 5.7 ppm.
When, instead of employing a nitrogen atmosphere
over the reaction mixture there are used instead carbon
dioxide, argon, or other gas inert to the reaction, or when
vacuum is employed (preferably lower than 2S cm. of mercury),
-- 19 --
1~ 4
good, light colored product of essentially the same physical
characteristics as previously mentioned results, in sLmilar
good yield. When vacuum is utilized it may often be desir-
able to lower the reaction temperature accordingly (usually
about 10-30C.) to prevent possible losses of reactants
and/or product. When a suitable inert gaseous a~mosphere is
not provided above the reactants, as when air is the gas
that is present, the N-coco alkyl neodecanoamide made is
darker in color and may be unsuitable for incorporation in a retail
detergent composition intended to impart antistatic proper-
ties to washed laundry.
An alternative reaction for the production of N-
higher coco alkyl neodecanoamide is the reaction of a gram-mole
of a neodecanoyl chloride, which is slowly added over a
period of about an hour to a gram-mole of coco alkyl amine
dissolved in a solvent medium of 700 ml. of diethyl ether
and a gram-mole of triethyl amine (which acts as a trap for
HCl). The coco alkyl amine is in a l-liter, 3-necked flask
fitted with a condenser with a Drierite tube, a thermometer,
a Chesapeake s~irrer and a dropping funnel, and the flask is
cooled by an ice bath.
After completion of addition of the neodecanoyl
chloride the ice bath is removed and the reaction mix is
allowed to come to room temperature, after which it is
stirred for an addltional hour. It is then transferred to a
Y
- 20 -
two-liter separatory funnel and is washed twice with water,
once with S~ aqueous hydrochloric acid and once with 5~
aqueous sodium hydroxide, followed by one or more washings
with distilled water until the product is neutral to pH
5 paper. Any remaining ether is removed by means of a steam
bath and the product is finished on a vacuum rotary evaporator.
The product made is water white to light amber in color, is
pure, and exhibits the inf rared and NMR spectra previously
described for the same product made by the condensation
10 method.
EXAMPLE 2
Essentially the same procedure as that described
A in Example 1 is followed but the reactants are Armak~tallow
amine (199 g.) and neodecanoic acid (121 g., prime grade,
15 95.2% pure). The reaction was conducted under nitrogen over
- a period of about eight hours at a temperature in the range
of 240-260C., and during that time eight ml. of water were
collected. The washing solutions employed were the same as
in Example 1 but four "final" washes with distilled water
20 were made to produce a tallow alkyl neodecanoamide that is
neutral to pH paper. The final traces of water and alcohol
were removed, utilizing a rotary evaporator. The yield was
159 grams of a light colored product (Gardner color = 2)
which included 2.5~ of the starting amine and 0.3~ of the
25 starting acid. The tallow alkyl neodecanoamide made has a
melting point of 15-17~C. and the infrared spectrum for it
* ~~r~ rK
is illustrated in FIG. 2. As was described in Example 1,
for the coco alkyl neodecanoamide, ~he tallow alkyl neodecano-
amide can also be made by the acid chloride proces , utilizing
equal molar proportions of neodecanoic acid and tallow alkyl
amine.
While the described condensation reaction, utilizing
heating of the reactants in a flask under inert atmosphere,
usually takes from 5 to 8 hours at a temperature in the
range of 180 to 320C. for the condensation process of this
example and others herein given, longer reaction times,
usually at lower temperatures, may be employed and shorter
reaction times, sometimes at higher temperatures, may be
utilized. A manufacturing apparatus for such quicker reactions
may be a thin film reactor or comparable equipment.
EXAMPLE 3
N-tallow alkyl neopentanoamide i5 made by reacting
51 grams of neopentanoic acid (obtained from Exxon Chemical
Americas) with 134 grams of tallow amine-TD (obtained from
Armak Chemical Company). The reaction is conducted in a
500 ml., 3-necked flask, equipped with a magnetic stirrer, a
condenser with a Dean-Stark trap, and a nitrogen inlet,
connected to a source of nitrogen. The flask was heated to
250C. and after five hours the heat was turned off and the
flask was allowed to set overnight. The product was transfer-
red to a heated separatory funnel and was sequentially
~r~ r~
-- 22 --
8.}~4
washed with aqueous alcoholic hydrochloric acid (53~ water,
44~ ethanol and 3% HCl), water-alcohol mixture (53% water,
47~ ethanol), aqueous alcoholic sodium hydroxide (53% water,
44~ ethanol and 3~ sodium hydroxide) and distilled water
(four washes), until the product was neutral to pH paper.
The product made is of a melting point of 38 to 39C.
EXAMPLE 4
The condensation reaction described in Examples 1
-3 is also practiced to make N-methyl neodecanoamide, N-
ethyl neodecanoamide, N-t-butyl neodecanoamide, N-octyl
neodecanoamide, N-myristyl neodecanoamide, N-hexadecyl
neodecanoamide (or N-palmityl neodecanoamide), N-oleyl
neodecanoamide, N-hydrogenated tallow neodecanoamide and
N-stearyl neodecanoamide. In all such reactions the apparatus
employed is like that described in Examples 1-3, a nitrogen
blanket is utilized, the time of reaction is from 5 to 8
hours and the reaction temperature is a suitable temperature
in the range of 180 to 300C. For the normally solid products
the washings are conducted in a heated separatory funnel and
heated washing a~ents are utilized.
The N-octyl neodecanoamide and the N-oleyl neodecano-
amide are both oily materials, like the N-tallow alkyl
neodecanoamide and N-coco alkyl neodecanoamide, and exhibit
greater adsorptions onto fabrics or fibrous materials than
do the other low melting neodecanoamides made, which allows
- 23 -
them to function more satisfactorily as antistats, useful
for incorporation in detergent compositions to impart anti-
static activity to washed laundry. The melting points of
the products made are listed below in Table 1, together with
the refractlve indices for some that have melting points
below 0C.
TABLE 1
Alk(en)yl (in N-alk(en)yl Melting Point (C.) Refractive Index
Neodecanoamide) (Nn 20C.)
Methyl ~ 0 1.4554
Ethyl ~ 0 1.4554
t-Butyl < 0
Octyl ~ 0 1.4596
Myristyl ~ 0 1.4612
15 Palmityl 37-38
Oleyl 5-6
Stearyl 35-40
Hydrogenated tallow 45-49
In addition to varying the alk(en)yl group of the
invented N-alk(en)yl neodecanoamides within the 8 to 20
carbon range, as described in this example and in Examples 1
and 2, the neoalkanoic acid moiety of the present amides may
also be changed. Thus, the condensation and acid chloride
reactionsof this example and Examples 1-3 may be practiced,
with the substitution for the neodecanoic acid of this
example and Examples 1 and 2 and for the neopentanoic acid
of Example 3, of other neoalkanoic acids of carbon atoms
contents in the range of 5 to 16, specifically neoheptanoic ac-
id, neononanoic acid, neododecanoic acid, neotridecanoic
acid and neotetradecan~ic acid. The productR within this
invention that are made by the described reactions, especially
the condensation reaction, as conducted under an inert gas
atmosphere and with acidic, basic and distilled water wash-
ings of the product to pH neutrality, are amides with anti-
static properties, which make them useful for the treatmentof laundry to decrease or prevent static clinging thereof
after machine drying. Especially preferred are the oily
appearing amides, such as those wherein the alk(en)yl group
is octyl, myristyl, oleyl or coco alkyl. However, the
tallow alkyl neodecanoamides and neopentanoamides are also
useful antistats and additionally possess fabric so~tening
properties, especially when employed in conjunction with
bentonite.
- 25 -
~Lf~8~ f
EXAMPLE 5
Component Percent
Sodium linear tridecylbenzene sulfonate 13.4
Sodium tripolyphosphate 24.0
5 Sodlum silicate (Na2O:SiO2 = 1:2.4~ 6.3
Sodium carbonate 4.5
Borax l.0
Fluorescent brighteners 0.3
Methyl cellulose 0-5
lO Sodium carboxymethyl cellulose 0.2
Sodium sulfate 49.6
Perfume 0.2
100.0
A spray dried detergent composition of the above
formula is made by spray drying an aqueous crutcher mix of
60% solids content in a conventional countercurrent spray
drying tower to produce spray dried detergent beads, less
perfume, which beads are subsequently perfumed by spraying
onto the surfaces thereof the formula proportion of liquid
perfume. The product is screened so that the particle sizes
thereof will be in the range of No's. lO to lO0, U.S. Sieve
Series. Then, desired proportions of oily neodecanoamides,
and N-tallow alkyl neopentanoamide are sprayed onto the
detergent composition beads to produce antistatic detergent
compositions. Instead of mixing the neoalkanoamide with
the detergent composition to make an antistatic detergent
- 26 -
composition, it may be added to the wash water, and sometimes
iB preferably added to the rinse. The effects of the anti-
stat materials are evaluated by washing test fabrics in top
loading Whirlpool washing machines and drying them in electric
automatic clothes dryers, after which they are tested for
static accumulations. A ballast load is employed in the
washing machine with the test swatches and with soil removal
index swatches, which are also present to check on any
possible negative effect of the antistat on soil removal
properties of the detergent composition. The ballast load
(five lbs.~ consists of 1/3 cotton terry face cloths; 1/3
cotton percale swatches (14" x 15"); and l/3 of 654 Dacron:
35% cotton swatches (14" x 15", without durable press finish).
The test swatches used for antistatic effect measurement are
14" x 15" and include one each of: Dacron double knit twill;
654 Dacron: 35% cotton permanent press; blue 65% Dacron: 35~
cotton permanent press; Banlon; acetate jersey; and nylon tricot.
The 80il removal index swatches measured 3" x 6" and four of
each type are present with the ballast laundry. The five
different types of such swatches are Test Fabrics Inc. soil
on nylon, Test Fabrics Inc. soil on cotton; Piscataway (New
Jersey) clay on cotton; Piscataway clay on 65% Dacron: 35
cotton cloth; and EMPA lOl oily soil on 65% Dacron: 35
cotton cloth.
After thorough cleaning of the washers and dryers,
~ ~r~
using 3A denatured alcohol, followed by air drying, the
washing machine is set for a 14 minute wash time, using 17
gallons of water at 120F. This "hot" wash is one uti~izing
the normal machine cycle, including a cold rinse with tap
water. The detergent composltion, containing the antistat
is added to the wash water after the machine is filled, the
machine is allowed to agitate for about ten seconds and then
the ballast load and the various test and soil removal index
swatches are separately added, while agitation is continued.
Subsequently the various fabrics are removed and placed in
the electric dryer, where they are dried over a period of
about two hours. The test swatches and two terry towels
from the ballast are then dried for an additional ten minutes
and the test swatches are then evaluated for static cling.
Prior to instrumental static measurements the test swatches
are hung in a low humidity room (25~ relative humidity)
overnight. The Blue 65 Dacron; 35 cotton swatch may be
examined for product spotting and the reflectance ~Rd)
values of the soil removal index swatches may be determined,
utilizing a reflectometer. Also, the cotton terry towels
from the ballast may be evaluated for softness. To determine
the static charges on the average test material, after
washing with the detergent composition containing antistat,
all of the static test swatches are rubbed in a controlled
manner, with wool, under controlled conditions, at a relative
humidity in the range of 25 to 30%, after which the electrostatic
charges on the swatches are measured and the measured electro-
static charges are averaged for each material, after which
the averages for the matexials are again averaged, resulting
in a static index. It has been found that differences of
as little as 6 index units (in kilovolts) are significant
and indicate that consumers will notice the difference in the
static clings of washed materials different in static indices
by six units.
The following table gives the static indices for
detergent compositions of this example, which are charged to
the washing machine at the rate of 100 grams per load (about
0.155%, on the basis of the wash water~. The additional
weights of neodecanoamide employed (O g., 3 g., 5 g., and
10 g.) are given in the table. The N-alk(en)yl neoalkanoamides
willbe sprayed onto the detergent beads as liquids at room
temperature or at elevated tmperatures, but can be applied in
solvents and may be mixed with the detergent as a powder,
alone or with a carrier. In cases wherein multiple determi-
nations were made, averages are given.
- 29 _
.4
TABLE 2
Alk(en)yl of 0 g./wash 3 g./wash 5 g./wash 10 g./wash
N-alkenyl (control)
Neodecanoamide
5 Methyl 38 - - 43
Ethyl 33 ~ 37 40
t-butyl - - - 41
Octyl 41 - 26
Coco alkyl (prime 42 26 14 5
neodecanoic acid
reactant~
Coco alkyl (technical 45 19 11
neodecanoic acid
reactant)
15 Myristyl 31 _ 11
Palmityl 43 - - 26
Tallow alkyl 41 - 21 16
Oleyl - 32 17 10
Stearyl - - - 28
20 Hydrogenated tallow 46 - _ 32
alkyl
Alk(en~yl (of N-
alk(en)yl neopenta-
noamide)
30 Tallow alkyl 46 - - 20
When skilled evaluators of fabric properties exam-
ine the test fabrics washed with control and experimental
detergent compositions for static cling they note no improvement
- 30 -
~2~ l4
~or the N-methyl neodecanoamide, N-ethyl neodecanoamide and
N-t-butyl neodecanoamide but significant improvements are
found for all the other n~odecanoamide~ reported in Table 2,
at the various concentrations indicated.
Reflectometer readings of the soil removal index
swatches showed no adverse effects on soil removal by the
tested antistats. Similarly, the blue cloth was not adversely
lightened in color, stained,or otherwise undesirably changed
in appearance, compared to a control.
When the other neoalkanoamides described in this
specification are tested in similar manner it will be found
that they too impart desirable an~static characteristics to
washed laundry. Similarly, when other detergent compositions
are utilized, such as non-phosphate detergent compositions
containing zeolite builder, and nonionic detergent composi-
tions,with or without phosphate builder and with or without
zeolite builder,similar results are also obtainable. In
addition to the particulate detergent compositions, liquid
detergent compositions may also be employed, in which the
neodecanoamide may be dissolved and/or dispersed, or with
whlch it may be added to the wash water in a washing machine.
One such formula includes 16~ of Neodol 25-7 (condensation
product of one mole of higher fatty alcohol of 12 to 15
carbon atoms with 7 moles of ethylene oxide), 5.54 of denatured
alcohol (3A), 3.14 of sodium linear dodecylbenzene sulfonate,
0.24 of fluorescent brightener, 34 of sodium formate, 14
'rr~le ~ f~
- 31 -
.. . , . .. _ _
(active ingredient basis) of soil release promoting agent
(Alkaril QCJ), 0.84 of enzymes, O.Ql% of blue dye, 0.4~ of
perfume, 10~ of N-coco alkyl neodecanoamide and 60~ of
water. It may also be desirable to incorporate about 5 to
104 of a hydrotrope, such as sodium benzene sulfonate, in the
formula to stabilize it against settllng out of the antistat.
EXAMPLE 6
Bentonite powder~ of a fineness of about No. 200,
U.S. Sieve Series, is agglomerated in known manner by tumbling
it in an inclined drum while spraying onto falling curtains
of the powder a relatively dilute aqueous sodium silicate
solution (about 2~) until agglomerate beads of about the
desired size result. Such beads are dried to acceptable
moisture content, which may be about 11~. Thereafter the
beads are screened to desired size range, such as No's. 10-
60, U.S. Sieve Series. N-tallow alkyl neodecanoamide, which
is an oily liquid at room temperature, is sprayed onto the
surfaces of the bentonite agglomerate beads while such beads
are being tumbled in an inclined drum, and the porous bentonite
beads absorb the neodecanoamide so that the resulting particulate
product remains free flowing. The proportion of neodecanoamide
in the product may be varied as desired but is desirably
about 20%.
When one part of the N-tallow alkyl neodecanoamide-
bentonite agglomerate product is mixed with three parts of
7~e m~
1~ a, r
the detergent composition of Example 5 (that without neoalkano-
amide) the resulting composition contains 204 of bentonite
and 5~ of the neoalkanoamide. Laundry washed with such
composition, at a concentration in the wash water of about
0.2%, is noticeably soft (especially important for cotton
items) and does not exhibit objectionable static cling
(important for synthetic items). The laundry softening
capability of the composition is greater than would have
been attributed to the bentonite content thereof and it is
considered that the N-tallow alkyl neodecanoamide, in the
presence of bentonite, either increases the bentonite soften-
ing activity or possesses independent softening characteristics.
Similar bentonite-neoalkanoamide products made with others
of the described neoalkanoamides do not exhibit the softening
increasing effect obtained with the N-tallow alkyl neodecano-
amide but they are useful for their antistatic properties,
in conjunction with the fabric softening activity of the
bentonite.
Instead of spraying liquid state neoalkanoamide
onto the bentonite agglomerate it may be sprayed onto the
finely divided powder before agglomeration, and may assist
ln agglomerating the bentonite. Also, for the neoalkano-
amides thatare in solid state at room temperature mixtures
of such in powdered form with bentonite powder may be made.
Alternatively, such materials may be liquefied by means of
heat or solvents, and may be applied to bentonite agglomerates
- 33 -
1~98.~4
or powders in such state.
Instead of employing the bentonite-neoalkanoamide
composition as an additive to a detergent composition to
make it softening and antistatic, that composition may be
used to treat already washed material, as in rinse water.
The neoalkanoamide, such as N-coco alkyl neodecanoamide, N-
myristyl neodecanoamide, N-oleyl neodecanoamide or N-octyl
neodecanoamide, may be added to either the wash water, rinse
water or other aqueous treating medium in a sufficient
concentration, normally in the range of 0.005 to 0.1~, to
impart antistatic properties to fibrous materials. In such
instances it will be normal to machine dry the fibrous
material or laundry, as in a tumbling automatic laundry dryer. It
is known that it is the act of drying the laundry while
moving it which promotes the development of static charges
thereon, which development is inhibited by treatment with a
neoalkanoamide of the present invention.
Although satisfactory antistatic action is obtained
when the present neoalkanoamides are employed in or with
built laundry detergent compositions, and fabric softening
is obtained from N-tallow alkyl neoalkanoamide when it is
employed with bentonite in or with detergent compositions,
better antistatic action is noted and better softening
effects for the neoalkanoamides are obtained with tallow
alkyl neodecanoamide (with bentonite) when such are employed
in rinsing steps, rather than in washing operations.
- 34 -
98;~1~
Wash cycle additive products of various types may
be made, including particulate, paste, gel, liquid and solid
tablet products, with the particulate material often prefer-
ably including inorganic builder salt, sodium sulfate,
agglomerated bentonite and perfume, as well as neoalkanoamide,
which preferably is coco alkyl neodecanoamide or tallow
alkyl neodecanoamide. One useful formula for such a particulate
product includes: 66.8~ of spray dried base beads made by
spray drying, to a moisture content of about 8~, a crutcher
mix containing 34.2 parts of water, 1.4 parts of fluorescent
brightener, 1 part of magnesium sulfate monohydrate, 0.4
part of sodium polyacrylate, 32 parts of zeolite 4A, 2.5
parts of white montmorillonite (or bentonite), 17 parts o4
sodium bicarbonate (during which spray drying half of the
sodium bicarbonate is converted to sodium carbonate), and
11.5 parts of soda ashi 21 parts of N-coco alkyl neodecanoamide
or N-tallow alkyl neodecanoamide; 0.2 part of perfume;and 12
parts of agglomerated bentonite (10-60 mesh).
Instead of the base materials that have been recited.for
application of the neoalkanoamide, other carriers may be
employed, such as Microcel C (synthetic calcium silicate),
sodium sulfate, soda ash or borax. Also, the neoalkanoamide
may be dissolved or dispersed in an aqueous, alcoholic or
other suitable solvent medium and applied alone or with
adjuvant(s). In some instances it may be desirable to
- 35 -
spray a normally liquid state neoalkanoamide onto surfaces
to be made antistatic.
A liquid preparation for addition to the rinse
water to render washed laundry antistatic may include about
91 parts of distilled water, about 1 part of perfume, about
0.3 part of nonionic detergent (preferably Neodol 25-7),
about 2 parts of isopropanol and about 5.7 parts of N-coco
alkyl neodecanoamide, N-tallow alkyl neodecanoamide or other
suitable neoalkanoamide within the invention.
EXAMPLE 7
A non-woven rayon sheet is impregnated with about
1.5 times its weight of coconut oil fatty acids diglyceride,
about 1/2 its weight of N-coco alkyl neodecanoamide (or N-
tallow alkyl neodecanoamide or other suitable neoalkanoamide)
and a desirable proportion (0.5%) of perfume. ~his product
is useful as an antistatic sheet to be added to a laundry
dryer, with the charge of sheeting to the dryer being such
that about 10 grams of the neoalkanoamide will be present
therein for every five to 10 pounds of laundry (dry basis).
Alternatively, the neoalkanoamide may be applied
to the tumbling drying laundry by other mechanisms, including
dispensing from a sponge or spraying or dripping liquid
state neoalkanoamide onto the tumbling laundry in the
automatic dryer.
In the above description and examples it is to be
- 36 -
12~
understood that mixtures of the invented neoalkanoamides may
be employed, usually with the adjustment of the composition
being such as to obtain most satisfactory antistatic action.
Also, application conditions and proportions may be adjusted
to obtain the desired results in the particular circumstances.
The invention has been described with respect to
various embodiments and illustrations thereof but is not to
be limited to these because it is evident that one of skill
in the art will be able to utilize substitutes and equivalents
without departing from the invention.
- 37 -
